CN102740950A - Method for separating a cleaned useful gas from a gas mixture and device for carrying out said method - Google Patents

Method for separating a cleaned useful gas from a gas mixture and device for carrying out said method Download PDF

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CN102740950A
CN102740950A CN2011800076876A CN201180007687A CN102740950A CN 102740950 A CN102740950 A CN 102740950A CN 2011800076876 A CN2011800076876 A CN 2011800076876A CN 201180007687 A CN201180007687 A CN 201180007687A CN 102740950 A CN102740950 A CN 102740950A
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carbon dioxide
valuable gases
liquid carbon
harmful substance
gas
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CN102740950B (en
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M.巴尔道夫
C.格雷伯
M.哈尼布思
G.齐默曼
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Siemens AG
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Siemens AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/70—Flue or combustion exhaust gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention relates to a method for separating a cleaned useful gas from a gas mixture substantially containing carbon dioxide, at least one useful gas, and at least one hazardous substance. The carbon dioxide is condensed, and the liquid carbon dioxide that is enriched with the hazardous substance is separated from the useful gas. The hazardous material is then separated from the liquid carbon dioxide by adsorption, and one part of the cleaned liquid carbon dioxide is introduced into the useful gas to absorb hazardous substances still contained in the useful gas.

Description

The method of the valuable gases of isolation of purified and the device of implementing this method from admixture of gas
The present invention relates to a kind of from admixture of gas the method for the valuable gases of isolation of purified, said admixture of gas contains carbon dioxide, at least a valuable gases, at least a harmful substance basically.
Because so-called greenhouse effects and the rising of relevant therewith global climate, the gas that in atmosphere, has discharged greenhouse effect gets more and more to such an extent that receive severe censure.Quite most greenhouse effect is owing to the aflame carbon dioxide (CO at fossil fuel 2).A large amount of fossil fuels for example burns in power station and industrial plant.
In order to offset this greenhouse effect, from the gas of power station and industrial process release, to isolate carbon dioxide as much as possible in the future.For this purpose, a large amount of R&D work is devoted to design the least possible or is not even discharged the equipment of carbon dioxide.Following purpose is all followed in all designs, if possible with as far as possible little energy consumption, from gas stream, isolates whole as far as possible and highly purified carbon dioxide, thereby at the gas that finally can in environment, discharge no carbon dioxide after the separation.
Yet; Except the carbon dioxide that requires to separate; In pending gas, also usually contain the material of not expecting, i.e. harmful substance (Schadstoffe), this material must produce and take out according to the type of the fossil fuel (fossil Brennstoff) of burning.What with regard to quantity, the most often occur is sulphur, mercury and their compound.That is to say, from gas, not only will isolate carbon dioxide, also will isolate harmful substance.
Up to the present, the harmful substance in the waste gas (like the waste gas that produces in the coal power plant), for example described sulphur compound and mercury compound, directly deposition is come out from gas phase.For example, the separation of hydrogen sulfide is undertaken by gas scrubbing.At this, gas spread lead through the absorption tower, liquid medium is absorbed with harmful substances in this absorption tower.Liquid absorption tower media is for example by aqueous alkanolamine, and particularly methyl-diethanolamine solution perhaps for example uses cold methanol in low-temp methanol method (Rectisol-Prozess).But the shortcoming of this moment particularly is used for the higher energy of method needs of gas scrubbing.
The effective of separating carbon dioxide and harmful substance possibly scheme be recorded among the disclosed after a while German patent application DE 10 2,009 035 389.5 from admixture of gas.According to this method, carbon dioxide freeze-outs from admixture of gas, that is to say, carbon dioxide is separated from admixture of gas as liquid phase.The harmful substance that in admixture of gas, contains is enriched in the liquid carbon dioxide at this moment.Then should be supplied in the absorber device by carbon dioxide liquid state, that carry harmful substances; The harmful substance that in this absorber, is included in the liquid carbon dioxide is adsorbed; And therefore separate from liquid carbon dioxide, the liquid carbon dioxide in absorber device exit does not contain hazardous substance basically or fully.
Because of cryogenic separation carbon dioxide CO 2And the valuable gases that obtains is pure.But verified now, not every harmful substance is enriched in CO in coacervation process 2In the liquid phase, but there is the harmful substance of certain residual share always to be included in the valuable gases.
Therefore, the objective of the invention is to openly to provide a kind of from admixture of gas the method for the valuable gases of isolation of purified, not only do not contain CO in this valuable gases basically 2, and do not contain hazardous substance basically.
In order to realize this purpose; Be provided with as follows in the method for the valuable gases of isolation of purified from the admixture of gas that contains carbon dioxide, at least a valuable gases and at least a harmful substance basically according to of the present invention; Cohesion (Kondensation) carbon dioxide; And with enrichment the liquid carbon dioxide of harmful substance separate with valuable gases; Adsorptivity is separated harmful substance from said liquid carbon dioxide then, and the liquid carbon dioxide that a part purifies is supplied to valuable gases still is included in the harmful substance in this valuable gases to absorb.
The inventive method provides that LOW TEMPERATURES goes out carbon dioxide from admixture of gas to be clean; Take out contained harmful substance by adsorbent equipment from the liquid carbon dioxide that carries harmful substances then, thereby when adsorption process finishes, have the liquid carbon dioxide of basic at least unharmful substance.Then the liquid carbon dioxide of this purification of a part is sent and is supplied to once more back to valuable gases.Caused advantageously at present the mixing once more of this valuable gases and liquid carbon dioxide that special owing to purify in the too high liquid carbon dioxide of degree of unsaturation, remaining harmful substance is enriched in the carbon dioxide in valuable gases.Then, with this liquid carbon dioxide be supplied to above-mentioned once more or another adsorbent equipment in, make and also take out the harmful substance that valuable gases absorbed " reaction " once more from the liquid carbon dioxide composition.
That is to say, be used for the harmful substance that admixture of gas contains as the absorber medium according to twice of the liquid carbon dioxide of the inventive method.For the first time, carry out in the scope that is absorbed in liquefied carbon dioxide of harmful substance, if use suitable carbon dioxide coacervation device carbon dioxide to be changed into liquid phase through cooling.For the second time, in the scope that the liquid carbon dioxide composition is back to valuable gases, use the carbon dioxide that always is in a liquid state, make from valuable gases, to be absorbed with the harmful substances composition as washing agent.That is to say that the liquid carbon dioxide that returns is similar to " liquid gas scrubbing agent ".
Therefore at last, the inventive method provides two purification phases of separating, that is, first be the valuable gases of carbonated and harmful substance not mutually, and second is the liquid carbon dioxide that does not contain hazardous substance mutually.
According to a particularly advantageous improvement project of the present invention, the carbon dioxide that liquid state is returned injects or sprays into valuable gases.To increase the surface of liquid carbon dioxide dramatically through atomizing, make that in gas phase (being valuable gases) and liquid phase (be liquid CO 2Drop) produces big exchange surface between.This has caused the very high absorptivity of residue harmful substance that is arranged in valuable gases, and this harmful substance can almost entirely be absorbed and take out.Obtained working method very efficiently thus; The separation that wherein carries the liquid carbon dioxide of harmful substances is carried out in the same container that enforcement is separated and harmful substance absorbs through the liquid carbon dioxide that returns, purify with harmful substance absorption for the second time, and said container is tower (Kolonne) or flash chamber (Flash Behaelter) or analog for example.That is to say; In this tower, introduce carbon dioxide and valuable gases cohesion, that carry harmful substances on the one hand; In this tower, implement separating of valuable gases and liquid carbon dioxide phase; The liquid carbon dioxide that will return simultaneously on the other hand, purify preferably sprays into or injects this tower, thereby purifies valuable gases fully.This returns, liquid carbon dioxide uses carbon dioxide initial provision, cohesion and that carry harmful substances to take out (abgezogen) then, and then supply gets into shared adsorbent equipment to separate harmful substance.
The valuable gases of separating can be any valuable gases, and it depends on the fossil fuel of burning.The mixture of example hydrogen, carbon monoxide, nitrogen, rare gas or above-mentioned gas.
The harmful substance that is produced also can be different in nature.Common harmful substance has sulphur, mercury and their compound or their mixture.
Except this method, the invention still further relates to the device that is used for isolating the valuable gases of purification from admixture of gas, said admixture of gas contains carbon dioxide, at least a valuable gases and at least a harmful substance basically.The inventive system comprises at least one carbon dioxide coacervation device; At least one is separated and is absorbed with the container of harmful substances; For example tower or flash chamber or analog; Be used for separating valuable gases from the liquid carbon dioxide that carries harmful substances; At least one adsorbent equipment is used for being absorbed in the harmful substance that the liquid carbon dioxide of separation contains, and Returning pipe is used for the liquid carbon dioxide that a part purifies is returned, preferably is back to tower to be absorbed in the residue harmful substance that contains in the valuable gases.A kind of this device can for example be incorporated in power station or any industrial equipment, and is used herein to gas purification.The all gas mixture that supply produces in the carbon dioxide coacervation device is chosen wantonly and is correspondingly being supplied after the preliminary treatment.In the carbon dioxide coacervation device, implement CO 2Cohesion.The mixture of valuable gases and liquid carbon dioxide is supplied then and is got in the container 4 that is fit to gas-liquid separation, in this container, is separated.The liquid carbon dioxide that carries harmful substances that from tower, takes out is supplied to adsorbent equipment then harmful substance is carried out the adsorptivity separation.The liquid carbon dioxide that from adsorbent equipment, takes out, purify part then refluxes through Returning pipe, and contacts the valuable gases of having separated with liquid carbon dioxide once more, thereby from valuable gases, takes out the residue pernicious gas.Returning pipe can directly be introduced in the container at this, that is to say, the carbon dioxide that returns is introduced the zone that has had the valuable gases of separation in the container once more, here " valuable gases washing " used the liquid carbon dioxide of absorbent effect to carry out.Except being back in the container, also there is following scheme, the liquid carbon dioxide and the valuable gases that purify are sent in " reaction vessel " suitable outside the tower together, make and implement the valuable gases washing at this.The operating temperature range of device is-70 ℃ to-10 ℃, preferred-60 ℃ to-30 ℃.
In an improvement project of the present invention, provide injection device or jetting device to be used for liquid carbon dioxide is injected or sprays into container or reactor, in this container or reactor (promptly for example at tower itself), from valuable gases, be absorbed with harmful substances.Exchange surface can regulated or change to degree through using the spraying of injection device or jetting device, promptly liquid CO 2The surface of phase, wherein big exchange surface is favourable for absorbing the residue harmful substance efficiently.
If injection device or jetting device are arranged in container self, so advantageously said device is arranged in the demister below that is arranged on tower, and valuable gases this demister of flowing through keeps liquid CO through this demister 2Drop.
Itself is preferably fixed-bed adsorber adsorbent equipment.For example preferably use active carbon, zeolite, alumina (aluminium oxide), polymer and analog as adsorbing medium (adsorbent), those adsorbents that wherein preferred use can be very easy to regenerate with big surface.At this moment, operate especially continuously thereby a plurality of adsorbent equipments are set, said a plurality of adsorbent equipments can be changed adsorption operations and regenerative operation in an alternating manner.This has realized in adsorption operations operation part adsorbent equipment, continuous purification CO thus continuously 2, and the adsorbent equipment of remainder is able to regeneration.As required, between two modes of operation, change, making always has the adsorbent equipment of some in operation in adsorption operations.
Other advantages of the present invention, characteristic and details hereinafter described embodiment and as figure in provide.
Accompanying drawing has shown that device 1 according to the present invention is used for from the valuable gases of admixture of gas 2 isolation of purified, and this admixture of gas forms gas stream, for example waste gas stream (for example using the power station or the stream of the waste gas in other industrial equipments of fossil fuel).This gas stream 2 contains carbon dioxide as basic mix ingredients, also contain at least a valuable gases such as hydrogen, and at least a harmful substance is like the harmful substance based on sulphur or mercury, like hydrogen sulfide (H 2S) or carbonyl sulfide (COS).Waste gas 2 at first gets into carbon dioxide coacervation device 3 as gas stream, and the temperature of cohesion takes place the carbon dioxide that waste gas 2 exists with gaseous form in waste gas before being cooled in this device.It changes into liquid phase.It is most of to be initially at the harmful substance that contains in the waste gas 2, but is not all, is dissolved in liquid CO 2Mutually.Then with these two phases, that is, the liquid carbon dioxide that carries the valuable gases of residue harmful substance and carry harmful substances is introduced container 4 for example in the tower 4, here is separated.Container area in the bottom is depositing the liquid carbon dioxide 5 that carries harmful substances, in the tower zone on top respectively at CO 2There is valuable gases 6 respectively in the horizontal plane top, and this valuable gases 6 is via being used for keeping the liquid CO that still is included in gas 2The demister 7 of drop takes out (abgezogen) and flows 8 as valuable gases.
As stated, liquid carbon dioxide 5 accumulates in the tower zone of bottom.According to the running temperature of apparatus of the present invention 1, in liquid carbon dioxide 5, also can there be the solid carbon dioxide of particle form about carbon dioxide coacervation device 3.But this running temperature should not cause forming the 3rd solid phase, thus the possible obstruction of the adsorbent equipment of having avoided will describing after a while.
With enrichment the liquid carbon dioxide 5 of harmful substance take out, and supply at least a, be in three kinds the adsorbent equipment 9 in the embodiment shown, in said device, being adsorbed property of the harmful substance taking-up that in liquid carbon dioxide 5, contains.As stated, the harmful substance that when carbon dioxide condenses, in gaseous mixture, contains automatically substantial enrichment liquid carbon dioxide mutually in.This is in the simple adsorptivity separation that has realized at present in adsorbent equipment 9.Adsorbent equipment 9 is preferably fixed-bed adsorber, and flow of liquid carbon dioxide is introduced wherein with pernicious gas.Can for example use active carbon, zeolite, aluminium oxide or polymer as adsorbing medium, decide according to the harmful substance that will adsorb or harmful substance mixture.
In the embodiment shown, three adsorbent equipments 9 are connected in parallel with each other.This provides following possibility; Only a part, for example two adsorbent equipments 9 carry out adsorption operations simultaneously; The 3rd adsorbent equipment 9 carries out regenerative operation with the regeneration adsorbing medium simultaneously, takes out thus and adsorbs harmful substance above that and make the adsorbing medium desaturation once more.To this, the pipeline and the valve of corresponding implementation handover operation is set with the known mode that still shows in detail.
Therefore, take out the liquid carbon dioxide 10 that no longer contains or almost no longer contain at present the purification of harmful substance from adsorbent equipment 9.
The liquid carbon dioxide that a part purifies delivers into tower 4 through Returning pipe 11 by pump 12 then once more, and obtains thin as far as possible spraying at this by injection device or jetting device 13.Injection or jetting device 13 are positioned at the zone near demister 7 bottoms, that is to say to be positioned at the tower zone that has valuable gases 6.The purification of carbon dioxide 10 that injects or spray into has caused pernicious gas and the CO that exists in relevant valuable gases 6 2Further absorption reaction between the small droplet, said CO 2Small droplet will absorb remaining harmful substance.The purification valuable gases 6 of flowing through demister 7 and then being removed is carbonated not only therefore, and does not contain hazardous substance.The carbon dioxide 10 that carries harmful substances now equally or once more that sprays into uses liquid carbon dioxide 5 original supply, that be positioned at tower bottom to take out then, and is supplied to adsorbent equipment 9 once more.
The part of not taken out by Returning pipe 11 in the carbon dioxide 10 that purifies is supplied to the post processing of suitable any kind.
As stated, if temperature the highest shoulding be-30 of the present invention ℃ should prevent that for fear of solidifying of carbon dioxide this temperature is lower than-60 ℃ so.The pressure of this method must be higher than the three phase point corresponding to carbon dioxide among the temperature, pressure figure basically.It is equivalent at least 5 crust.Obviously, corresponding operation parameter is used according to existing admixture of gas composition and relevant harmful substance with used adsorbing medium.

Claims (11)

1. the method for the valuable gases of isolation of purified from admixture of gas; Said admixture of gas contains carbon dioxide, at least a valuable gases and at least a harmful substance basically; Wherein condense carbon dioxide; And with enrichment the liquid carbon dioxide of harmful substance separate with valuable gases, adsorptivity is separated harmful substance from said liquid carbon dioxide then, and the liquid carbon dioxide that a part purifies is supplied to valuable gases still is included in the harmful substance in this valuable gases to absorb.
2. according to the method for claim 1, it is characterized in that, said liquid carbon dioxide is injected or sprays into said valuable gases.
3. according to the method for claim 1 or 2, it is characterized in that said liquid carbon dioxide and being separated in the container of said valuable gases that carries harmful substances carried out, wherein the liquid carbon dioxide with said purification is supplied in this container.
4. each method is characterized in that in the aforementioned claim, and as the valuable gases separation is hydrogen, carbon monoxide, nitrogen, inert gas or their mixture.
5. each method is characterized in that in the aforementioned claim, and as the harmful substance separation is sulphur, mercury, their compound or their mixture.
6. be used for isolating the device of the valuable gases of purification from admixture of gas; Said admixture of gas contains carbon dioxide, at least a valuable gases and at least a harmful substance basically; Said device comprises: at least one carbon dioxide coacervation device (3); At least one is used to separate valuable gases (6; 8) with the container (4) that carries the liquid carbon dioxide (5) of harmful substances; At least one is used for absorbing the adsorbent equipment (9) of the harmful substance of the liquid carbon dioxide (5) that is included in separation, and is used for sending, preferably return to the liquid carbon dioxide (10) that a part purifies back to Returning pipe (11) that said container (4) is used for absorbing the remaining harmful substance that is included in said valuable gases (6).
7. according to the device of claim 6, it is characterized in that, be used for injecting or the injection or the jetting device (13) that spray into said liquid carbon dioxide (10) preferably is arranged on said container (4).
8. according to the device of claim 7, it is characterized in that said injection or jetting device (13) are set in place in the below of the demister (7) of said container (4).
9. according to each device in the claim 6 to 8, it is characterized in that the container (4) that is used to separate gas phase and liquid phase is tower or flash chamber.
10. according to each device in the claim 6 to 9, it is characterized in that said adsorbent equipment (9) is a fixed-bed adsorber.
11. according to each device in the claim 6 to 10, it is characterized in that, a plurality of adsorbent equipments (9) be set, convertible in an alternating manner adsorption operations of this adsorbent equipment (9) and regenerative operation.
CN201180007687.6A 2010-01-28 2011-01-20 Method for separating a cleaned useful gas from a gas mixture and device for carrying out said method Expired - Fee Related CN102740950B (en)

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